Applied chemistry

UNIT II: Corrosion Science

Corrosion – electrochemical corrosion: chemical corrosion: Pilling-Bedworth
ratio - types of oxide layer (stable, unstable, volatile, porous) - hydrogen
evolution and oxygen absorption mechanism for electrochemical corrosion -
mechanism for rusting of iron. Electrochemical corrosion: Galvanic corrosion -
differential aeration corrosion (pitting, waterline and pipeline). Galvanic series -
applications. Factors influencing corrosion: nature of metal and environment.
Corrosion control methods: sacrificial anode method - impressed current
cathodic protection method- Protective coating: paint- constituents and
functions.
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ONE MARK QUESTIONS WITH ANSWER
1. All the metals above hydrogen in the electrochemical series undergo …………..reaction.
A. Oxidation B) Reduction C) Redox D) Neutralization
2. If the volume of metal oxide layer formed is less than the volume of the metal consumed,
then the oxide layer is
A) Porous and non-protective B) Non-porous and non-protective C) Porous and protective
D) Non-porous and protective
3. Pilling Bedworth rule is concerned with
A) Temperature of the oxide layer B) Volume of the oxide layer C) Density of the oxide
Layer D) Colour of the oxide layer
4. The formation of hydrogen gas inside the metal leads to
A) Galvanization B) Caustic embrittlement C) Hydrogen embrittlement D) Metal degradation
5. Bolt and nut made of same metal is preferred to avoid ----- corrosion
A) Chemical B) Stress C) Pitting D) Galvanic
6. A gas evolved during the decarburization is
A) Hydrogen B) Bromine C) Nitrogen D) Methane
7. Electrochemical corrosion takes place in
A) Cathodic area B) Near cathode C) Near anode D) Anodic area
8. An example for volatile metal oxide layer is
A) Fe2O3 B) MoO3 C) Fe3O4 D) FeO
9. Most suitable corrosion control technique to protect the buried iron pipelines is
A) Sacrificial anode B) Impressed current cathode C) Electroplating D) Cathodic inhibit
10. The corrosion in ship hulls is prevented by
A) Sacrificial anode method B) Impressed current method C) Deaeration method
D) Deactivation method
11. Differential metal corrosion is otherwise known as
A) Galvanic corrosion B) Pitting corrosion C) Pipeline corrosion D) Waterline corrosion
12. Which of the following is essential in electroless plating?
A) Oxidizing agent B) Reducing agent C) Anode D) Electrical energy
13. Choose a metal from the list can act as a best anode for corrosion protection of Iron
according to their emf value.
A) Zn = -0.76 B) Al = -1.67 C) Pb = -0.13 D) Mg = -2.36
14. Predict the type of oxide layer formed when chromium exposed to atmospheric oxygen
A) Stable oxide layer B) Unstable oxide layer C) Volatile oxide layer D) Porous oxide layer
15. Select the type of corrosion occur in metal containing other metal impurities
A) Differential aeration B) Galvanic corrosion C) Crevice corrosion D) Pitting corrosion.
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1. Define corrosion. Give example and types.
Corrosion:
“Corrosion can be defined as a process of gradual destruction or
deterioration of metals or alloys by the chemical or electrochemical
reaction with its environment”.
Example:
Rusting of iron (Fe + O2 → Fe3O4)
Types:
Based on the environment corrosion is classified into two types.
1. Chemical or dry corrosion
2. Electrochemical or wet corrosion

2. Distinguish between dry corrosion and wet corrosion.

SI.No Dry or Chemical corrosion Wet or Electrochemical

corrosion
1. It occurs in dry state It occurs in presence of moisture
or electrolyte
2. It follows adsorption mechanism It follows the mechanism of
electro chemical reaction
3. Corrosion produce accumulate Corrosion occurs at anode while
on the same spot, where products gather at cathode
corrosion occurs
2. Explain the consequences of corrosion.

1. Formation of corrosion product over machinery reduces the efficiency of machine.

2. The products get contaminated due to corrosion.
3. The corroded equipment must be replaced frequently.
4. Plant gets failure due to corrosion.
5. It is necessary for over design to compensate for the corrosion.
6. Corrosion releases toxic products, health hazards, etc.

3. State and explain pilling and bed worth rule. (Or) What is pilling – Bed
worth ratio?
Pilling – Bed worth rule:
According to Pilling – Bed worth rule, if the volume of the oxide layer
formed is less than the volume of metal; the oxide layer is porous and hence
non protective.
Example: Oxides of alkali and alkaline earth metals such as Na, Mg, Ca etc.

On the other hand if the volume of oxide layer formed is greater than the
volume of the metal; the oxide layer is non porous and protective.
Example: Oxides of heavy metals such as Pb, Sn etc.

Pilling – Bed worth ratio

The ratio of the volume of the oxide formed to the volume of the metal
consumed is called “Pilling – bed worth ratio”.

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4. What is hydrogen embrittlement? Where it is caused?
Hydrogen embrittlement is the effect of atomic hydrogen on metals at ordinary
temperature causing cracks and blisters by occupying the voids of the metals.
When metals contact to H2S at ordinary temperature causes evolution of
atomic hydrogen.
Fe + H2S FeS +2H
This atomic hydrogen diffuse readily into the metal and collects in the
voids, where it recombines to form molecular hydrogen
H+H H2
Collection of these gases in the voids causes cracks and blisters on the
metal. This process is called hydrogen embrittlement.

5. What is „decarburization‟?

Thermal decomposition of hydrogen

H2 2H
Formation of Methane gas
C + 4H CH4
The process of decrease in carbon content in steel is termed as
“decarburization” of steel.

6. What is electrochemical corrosion? (Or) What is galvanic cell corrosion?

(Or) State the two conditions for wet corrosion (electrochemical
corrosion) to take place.

Wet corrosion or electrochemical corrosion occurs in the following conditions.

(i) When two dissimilar metals or alloys are in contact with each other in
the presence of an aqueous solution or moisture.
(ii) When a metal is exposed to varying concentration of oxygen or any
electrolyte.
Under the above condition, one part of the metal act as anode and another
part act as cathode.
Example: In Zn-Fe couple, Zn acts as anode undergoes corrosion.

7. What is concentration cell corrosion? (OR) Differential aeration

corrosion? Give an example.

Concentration cell corrosion:

The concentration cell corrosion occurs when a metal is exposed to
varying concentration of oxygen or any electrolyte on the surface of the
base metal.
The more aerated part becomes cathodic. The metal part inside the
solution is less aerated and thus become anodic and suffers corrosion.
Examples for this corrosion are
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 1. Pitting or localized corrosion.
2. Crevice corrosion
3. Pipeline corrosion
4. Corrosion on wire fence
8. What is pitting corrosion?
Pitting corrosion:
Pitting is a localized attack,
resulting in the formation of a
hole around which the metal is
relativity unattacked.
Example:
Metal area covered by a
drop of water, sand, dust, scale
etc., Let us consider a drop of
water or aqueous NaCl resting on
a metal surface, the area covered
by the drop of water acts as an
anode due to less oxygen concentration and suffer corrosion. The uncovered
area acts as cathode due to high oxygen concentration.

9. How does the galvanic corrosion occur? How to prevent the galvanic
corrosion?
When two dissimilar metals or alloys are in
contact with each other in the presence of an
aqueous solution or moisture galvanic corrosion
occurs. It can be minimized by the using the
following steps.
1. Selecting the metals as close as possible
in the electrochemical series.
2. Providing smaller area for cathode and
larger area for anode.
3. Inserting an insulating material between the two metals.

10. What is pipeline corrosion? (Or) Explain what happens if a pipeline is

partially buried under the earth surface?

Differential corrosion occurs at different

parts of pipeline when it is partially buried
under the earth surface.

Buried pipelines or Cables passing from

one type of soil to another, ie., from clay
(less aerated) to cinders (more aerated) get
corroded due to differential aeration.

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11. Bolt and nut made of same metal is preferred in practice. Why?

Bolt and nut made of same metal is preferred in practice in order to avoid
galvanic type corrosion.

12. What are protective coatings? How are they classified?

Protective coatings:
Protective coatings are used to protect the metals from corrosion. It acts
as a physical barrier between the coated metal surface and the environment.

Classification: Protective coatings

Inorganic Coating Organic Coatings

Metallic coatings Non-metallic coatings Paints

13. What is paint and what are the requisites of a good paint?
Paint:
Paint is a mechanical dispersion of one or more finely divided pigments
in a medium. When paint is applied to a metal surface, the thinner
evaporates, while the vehicle undergoes slow oxidation forming a
pigmented film.
Requisites of a good paint:
1. It should spread easily on the metal surface.
2. It should have high hiding power. 3. It should not crack on drying.
4. It should adhere well to the surface. 5. The colour of the paint should be
stable. 6. It should be a corrosion and water resistant.
7. It should give a glossy film.

14. What is water line corrosion? Explain with an example?

This type of corrosion occurs when a metal is exposed to varying
concentration of oxygen or any electrolyte or water on the surface of the
base metal. Here the metal above the water is more aerated and become
cathodic, the part below the water is less aerated and become anodic.

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15. Describe the mechanism of dry (or) chemical corrosion by oxygen

Chemical corrosion by oxygen

 Oxidation corrosion is brought about by the direct attack of oxygen at low or

high temperatures on metal surface in the absence of moisture. Alkali
metals (Li, Na, K, etc.)

 Alkaline-earth metals (Mg, Ca, Sn, etc.) are rapidly oxidized at low
temperature. At high temperature, almost all metals (except, Ag, Au and Pt)
are oxidized.

Mechanism

(i) Oxidation occurs first at the surface of the metal resulting in the

formation of metal ions

(M2+), which occurs at the metal /oxide interface.

M M2+ + 2e−

(ii) Oxygen changes to ionic form (O2−) due to the transfer of electron from

metal, which occurs at the oxides film/environment interface.

½ O2 + 2e− O2−

(iii) Oxide ions react with the metal ion to form the metal-oxide film.

M + ½ O2 M2+ + O2− ≡ MO
(Metal-oxide film)

Once the metal surface is converted to a monolayer of metal-oxide, for further

corrosion (oxidation) to occur, the metal ion diffuses outward through the
metal-oxide barrier. Thus the growth of oxide film commences perpendicular to
the metal surface.
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16. When does the electrochemical corrosion occur? Describe the

mechanism of electrochemical corrosion

Wet corrosion occurs under the following conditions:

1. When two dissimilar metals or alloys are in contact with each other in
the presence of an aqueous solution or moisture.
2. When a metal is exposed to varying concentration of oxygen or any
electrolyte.

Mechanism of wet corrosion:

Under the above conditions, one part of the metal becomes anode and
another part as cathode.
(i) At anode:
In anodic part, oxidation (or) dissolution of metal occurs
M  M2+ + 2e-
(ii) At cathode:
In cathodic part reduction reaction occurs, which depends on nature of the
corrosive environment.

(a) Acidic environment:

If the corrosive environment is acidic, hydrogen evolution occurs at cathode
part.
2H+ + 2e-  H2 
(b) Neutral environment:
If the corrosive environment is slightly alkaline (or) neutral, hydroxide
ion forms at cathodic part.
½ 02 + 2e- + H2O  2OH-
Thus the metal ions (from anodic part) and non – metallic ions (from
cathodic part) diffuse towards each other through conducting medium and
form a corrosion product between anode and cathode.
i. Mechanism of electrochemical corrosion by hydrogen evolution type

“All metals above hydrogen in the electrochemical series have a

tendency to get dissolved in acidic solution with simultaneous evolution of

hydrogen gas”

Fig: Hydrogen evolution type corrosion

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For example:
When iron metal contacts with non-oxidizing acid like HCl, H2 evolution
occurs.
At Anode
Iron undergoes dissolution to give Fe2+ ions with the liberation of electrons.
Fe Fe2+ + 2e− (Oxidation)
At Cathode
The liberated electrons flow from anodic to cathodic part, where H+ ions get
reduced to H2.
2H+ + 2e− H2 ↑ (Reduction)

ii. Absorption of oxygen (or) Formation of hydroxide ion type corrosion:

The surface of iron is usually, coated with a thin film of iron oxide. However, if
the oxide film develops some crack will
come and anodic areas are created on the
surface while the remaining part acts as
cathode.

Example:

When iron metal contacts with a neutral

solution of an electrolyte in pressure of
oxygen, OH ions are formed.

At anode:
Iron dissolves as Fe2+ with the liberation of electrons.

Fe  Fe2+ + 2e- (Oxidation)

At cathode:
The liberated electrons flow from anodic to cathodic part through metal, where
the electrons are taken up by the dissolved oxygen to form OH ions.

½ O2 + H2 O + 2e-  2OH-

Thus, the net corrosion reaction is

Fe2+ +2OH-  Fe(OH)2 

If enough O2 is present Fe(OH)2 is easily oxidized to Fe (OH)3, a rust (Fe2 O3,

H2O).

4Fe(OH)2 + O2 + 2H2 O  4 Fe(OH)3

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17. What is differential aeration corrosion? Write its mechanism. Give any
illustrations that show differential corrosion. (or) Discuss briefly on
differential aeration corrosion

Definition: Differential aeration corrosion is concentration cell corrosion,

occurs when a metal is exposed to varying concentration of oxygen (or) air.

Differential aeration corrosion occurs when a metal surface is exposed to

differential air concentrations or oxygen concentrations. The part of the metal
exposed to higher oxygen concentration acts as cathodic region and part of the
metal exposed lower oxygen concentration acts as anodic region. Consequently,
poorly oxygenated region undergoes corrosion.
At the anode (less O2 concentration), M  Mn+ + ne
At the cathode (more O2 concentration), H2O + ½ O2 + 2e-  2OH-

Examples:
a) Pitting or localized corrosion.
b) Crevice corrosion.
c) Pipeline corrosion.
d) Corrosion on wire fence

18. Explain the sacrificial anode and impressed current cathodic

techniques for the prevention of corrosion. (6 marks)

Sacrificial anode method

In this method, the metallic structure to be protected is made cathode by
connecting it with more active metal (anodic metal). Hence, all the corrosion
will concentrate only on the active metal. The artificially made anode thus
gradually gets corroded protecting the original metallic structure. Hence this
process is otherwise known as sacrificial anodic protection.

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Aluminium, Zinc and Magnesium are used as sacrificial anodes.

Applications of Sacrificial Anodic Protection

This method is used for the protection of ships and boats. Sheets of Mg or Zn
are hung around the hull of the ship. Zn or Mg will act as anode compared to
iron (ship or boat is made of iron), so corrosion concentrates on Zn or Mg.
Since they are sacrificed in the process of saving iron, they are called sacrificial
anodes.

Impressed current cathodic protection

In this method, an impressed current is applied in the opposite direction
of the corrosion current to nullify it, and the corroding metal is converted from
anode to cathode. This can be done by connecting negative terminal of the
battery to the metallic structure, to be protected, and positive terminal of the
battery is connected to an inert anode.

Inert anodes used for this purpose are graphite, platinised titanium. The
anode is buried in a “back fill” (containing mixture of gypsum, coke, breeze,
sodium sulphate). The “back fill” provides good electrical contact to anode).
Applications of Impressed Current Protection
Structures like tanks, pipelines, transmission line towers, underground water
pipe lines, oil pipe lines, ships, etc., can be protected by this method.

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19. Explain the various factors which influence the rate of corrosion of a
metal (or) what are the factors which influence chemical corrosion and
electrochemical corrosion? (12 marks)

The rate and extent of corrosion mainly depends on

(i) Nature of the metal
(ii) Nature of the environment.

Nature of the Metal

(a) Position in EMF Series
The extent of corrosion depends on the position of the metal in the emf series.
Metals above the hydrogen in emf series get corroded vigorously. Lower the
reduction potential, greater is the rate of corrosion. When two metals are in
electrical contact, the more active metal (or the metal having high negative
reduction potential) undergoes corrosion. The rate and severity of corrosion
depends on the difference in their positions in the emf series. Greater the
difference faster is the corrosion rate.
(b) Relative Areas of the Anode and Cathode
The rate of corrosion will be more, when the cathodic area is larger. When the
cathodic area is larger, the demand for electrons will be more and this results
in an increased rate of corrosion (dissolution) of metals at anodic area.
(c) Purity of the Metal
The 100% pure metal will not undergo any type of corrosion. But, the
presence of impurities in a metal creates heterogeneity and thus galvanic cells
are set up with distinct anodic and cathodic area in the metal. Higher the
percentage of impurity, faster is the rate of corrosion of the anodic metal. The
effect of impurities on the rate of corrosion of zinc is given below.

(d) Over Voltage or Over Potential

The over voltage of a metal in the corrosive environment is inversely
proportional to corrosion rate.

(e) Nature of the surface film

The nature of the oxide film formed on the metal surface decides the extent of
corrosion which can be decided by Pilling-Bedworth rule. In the case of alkali
and alkaline earth metals such as Mg, Ca, etc. form oxide, whose volume is
less than the volume of the metal. Hence the oxide film will be porous and non-
protective and bring about further corrosion. But in heavy metals like Al, Cr,
etc. form oxide, whose volume is greater than that of the metal. Hence the
oxide film will be non-porous and protective and prevents further corrosion.
(f) Nature of the Corrosion Product
If the corrosion product is soluble in the corroding medium, the corrosion rate
will be faster. Similarly, if the corrosion product is volatile (like MoO3 on Mo
surface), the corrosion rate will be faster.
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Nature of the Environment

(a) Temperature

The rate of corrosion is directly proportional to temperature. This is because,

the rate of chemical reaction and the rate of diffusion of the ions increases with
rise in temperature. Hence the rate of corrosion increases with temperature.

(b) Humidity
The rate of corrosion will be more, when the humidity in the environment is
high. The moisture acts as a solvent for the oxygen in the air to produce the
electrolyte, which is essential for setting up a corrosion cell.

(c) Presence of Corrosive Gases

The acidic gases like, CO2, SO2, H2S and fumes of HCl, H2SO4, etc., produce
electrolytes, which are acidic and increases the electrochemical corrosion.

(d) Presence of Suspended Particles

Particles like, NaCl, (NH4)2SO4 along with moisture act as powerful electrolytes
and thus accelerate the electrochemical corrosion.

(e) Effect of pH
The rate of corrosion can also be reduced by increasing the pH of the solution
by adding alkali. Thus the rate of corrosion will be maximum when the
corrosive environment is acidic. i.e. pH is less than 7.

20. What is paint? What are the constituents of paint and their functions?

Paint:
Paint is a mechanical dispersion of one or more finely divided pigments
in a medium. When paint is applied to a metal surface, the thinner evaporates,
while the vehicle undergoes slow oxidation forming a pigmented film.
Requisites of a good paint:
1. It should spread easily on the metal surface.
2. It should have high hiding power.
3. It should not crack on drying.
4. It should adhere well to the surface.
5. The colour of the paint should be stable.
6. It should be a corrosion and water resistant.
7. It should give a glossy film.
Constituents and their functions of paint
1. Pigments2. Vehicle (or) drying oil 3. Thinners (or) solvents 4. Extenders
(or) fillers 5. Driers 6. Plasticisers 7. Anti-skinning agents
1. Pigments
Pigments are solid and colour producing substances in the paint.
Functions
(i) It gives colour and opacity to the film.
(ii) It also provides strength to the film.
(iii) It protects the film by reflecting the destructive uv rays.
(iv) It increases weather resistance of the film.
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2. Vehicle (or) Drying Oil
This is a non-volatile portion of a medium and film forming constituent of the
paint. These are high molecular weight fatty acids present in vegetable and
animal oils.
Functions
(i) They form a protective film by the oxidation and polymerisation of the oil.
(ii) They hold the pigment particles together on the metal surface.
(iii) They impart water repellency, toughness and durability to the film.
3. Thinners (or) Solvents
This is a volatile portion of a medium. It easily evaporates after application of
the paint.
Functions
(i) It reduces the viscosity of the paint, so that it can be easily applied on the
surface.
(ii) It dissolves the oil, pigments, etc. and produces a homogeneous mixture.
(iii) It increases the elasticity of the film.
(iv) It increases the penetrating power of the vehicle.
4. Extenders (or) fillers
These are white (or) colourless pigments.
Functions
(i) It reduces the cost of the paint.
(ii) It retards the settling of the pigment in all paints.
(iii) It modifies the shades of the pigments.
(iv) It prevents shrinkage and cracking.
5. Driers
These are the substances, used to accelerate the process of drying.
Functions
(i) They act as oxygen-carriers (or) catalysts.
(ii) They provide oxygen, which is essential for oxidation, polymerisation of
drying oil.
6. Plasticisers
These are chemicals added to the paint to provide elasticity to the film and to
prevent cracking of the film.
Example: Triphenyl phosphate, tricresyl phosphate, etc
7. Anti – Skinning Agents
These are chemicals added to the paint to prevent gelling and skinning of the
paint.
Example: Polyhydroxy phenol.

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